JPWO2020071380A1 - Compositions for thermal cycle systems and thermal cycle systems - Google Patents

Abstract

A composition for a thermodynamic cycle system containing 1,1,2-trifluoroethylene, which comprises a working medium having a cycle performance that can replace R410A while suppressing the influence on global warming. And the provision of a thermodynamic cycle system using the composition. Contains at least one compound selected from 1,1,2-trifluoroethylene, CF3I and hydrofluorocarbons, hydrofluoroolefins and hydrocarbons other than 1,1,2-trifluoroethylene, and has a temperature gradient of 7 ° C. or lower. A thermal cycle system having a working medium for the thermal cycle and using the composition for the thermal cycle system.

Description

The present invention relates to a composition for a thermal cycle system and a thermal cycle system using the composition.

Conventionally, working media for heat cycle systems such as refrigerants for refrigerating machines, refrigerants for air conditioners, working media for power generation systems (waste heat recovery power generation, etc.), working media for latent heat transport equipment (heat pipes, etc.), secondary cooling media, etc. As the chlorofluorocarbon (CFC) such as chlorotrifluoromethane and dichlorodifluoromethane, and hydrochlorofluorocarbon (HCFC) such as chlorodifluoromethane have been used. However, CFCs and HCFCs have been pointed out to have an impact on the ozone layer in the stratosphere and are currently subject to regulation.

For this reason, difluoromethane (HFC-32), tetrafluoroethane, and pentafluoroethane (HFC-125), which have less effect on the ozone layer, can be used as working media for thermal cycle systems instead of CFCs and HCFCs. Hydrofluorocarbons (HFCs) such as CFCs have come to be used. For example, R410A (pseudo-azeotropic mixed refrigerant having a mass ratio of HFC-32 and HFC-125 of 1: 1) and the like are conventionally widely used refrigerants. However, it has been pointed out that HFCs may cause global warming.

R410A has been widely used in ordinary air-conditioning equipment such as so-called package air conditioners and room air conditioners due to its high refrigerating capacity. However, the global warming potential (GWP) is as high as 2088, and therefore the development of a low GWP operating medium is required. At this time, it is required to develop an operating medium on the premise that R410A is simply replaced and the equipment that has been used so far is used as it is.

Recently, hydrofluoroolefins, which have a carbon-carbon double bond and are easily decomposed by OH radicals in the atmosphere, are a working medium having a small effect on the ozone layer and a small effect on global warming. Expectations are high for olefins (HFOs), that is, HFCs with carbon-carbon double bonds. In the present specification, unless otherwise specified, saturated HFCs are referred to as HFCs and are used separately from HFOs. HFCs may also be specified as saturated hydrofluorocarbons.

As a working medium using HFO, for example, Patent Document 1 describes a technique relating to a working medium using 1,1,2-trifluoroethylene (HFO-1123), which has the above-mentioned characteristics and can obtain excellent cycle performance. Is disclosed. In Patent Document 1, further, for the purpose of improving the nonflammability, cycle performance, etc. of the working medium, an attempt is made to combine HFO-1123 with various HFCs and HFOs to obtain a working medium.

Here, HFO-1123 is known to self-decompose in the presence of an ignition source under high temperature or high pressure. Therefore, various studies have been made to add a stabilizer that suppresses autolysis of HFO-1123, _{and a working medium containing CF 3} I as this stabilizer is also known (for example, Patent Documents 2 and 2). 3).

International Publication No. 2012/157964 International Publication No. 2015/125885 JP-A-2018-104566

However, by using HFO-1123 and CF ₃ I together, it is possible to utilize the high thermodynamic performance of HFO-1123 while suppressing self-decomposition, _{but when the content of CF 3} I increases, the working medium The temperature gradient of the above becomes large, and the composition fluctuates in the thermal cycle system, which may cause a problem in practical use.

Therefore, in the present invention, in a _{composition for a thermodynamic cycle system including HFO-1123 and CF 3} I, heat including an operating medium having a temperature gradient within a predetermined range while effectively utilizing its high thermodynamic cycle performance. An object of the present invention is to provide a composition for a cycle system and a thermodynamic cycle system using the composition.

Further, the present invention is a composition for a thermodynamic cycle system including a working medium for a thermodynamic cycle, which has properties such as suppression of an influence on global warming, impartation of non-combustible properties, and substitutability for R410A, R407C and R404A. It is also an object to provide a thermodynamic cycle system using the composition.

The present invention provides a composition for a thermodynamic cycle system and a thermodynamic cycle system having the configurations described in the following [1] to [9].

[1] 1,1,2-trifluoro-ethylene, include CF ₃ I and hydrofluorocarbon, the 1,1,2 least one compound selected from the hydrofluoroolefin and hydro carbon other than trifluoroethylene, temperature A composition for a thermal cycle system, which comprises a working medium for a thermal cycle having a gradient of 7 ° C. or lower.
[2] The composition for a thermodynamic cycle system according to [1], wherein the hydrofluorocarbon is difluoromethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane or fluoroethane.
[3] The composition for a thermodynamic cycle system according to [1] or [2], wherein the hydrofluorocarbon is difluoromethane.
[4] The composition for a thermodynamic cycle system according to [1] or [2], wherein the hydrofluorocarbon is pentafluoroethane.
[5] The composition for a thermodynamic cycle system according to [1] or [2], wherein the hydrofluorocarbon is 1,1,1,2-tetrafluoroethane.
[6] The composition for a thermodynamic cycle system according to [1] or [2], wherein the hydrofluorocarbon is fluoroethane.
[7] The hydrofluoroolefin is 2,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene, trans. The composition for a thermal cycle system according to any one of [1] to [6], which is -1,2-difluoroethylene or cis-1,2-difluoroethylene.
[8] The composition for a thermodynamic cycle system according to any one of [1] to [7], wherein the hydrocarbon is propane.
[9] The composition for a thermodynamic cycle system according to any one of [1] to [8], wherein the content of the hydrofluorocarbon is 10 to 30% by mass.
[10] The composition for a thermodynamic cycle system according to any one of [1] to [9], which is nonflammable.
[11] A thermodynamic cycle system using the composition for a thermodynamic cycle system according to any one of [1] to [10].
[12] The heat cycle system according to [11], wherein the heat cycle system is a refrigerating / refrigerating device, an air conditioning device, a power generation system, a heat transport device, or a secondary cooler.

According to the composition for a thermodynamic cycle system of the present invention, R410A contains a mixing working medium having a low temperature gradient while exhibiting the excellent cycle performance of 1,1,2-trifluoroethylene (HFO-1123). , A composition for a thermodynamic cycle system that can replace R407C and R404A.

According to the thermal cycle system of the present invention, the composition for the thermal cycle system of the present invention can be applied to obtain a thermal cycle system having both high cycle performance and durability.

It is a schematic block diagram which showed the refrigerating cycle system which is an example of the thermal cycle system of this invention. It is a cycle diagram which described the state change of the working medium for a thermal cycle in the refrigeration cycle system of FIG. 1 on the pressure-enthalpy diagram.

Hereinafter, the present invention will be described in detail with reference to embodiments.
In the present specification, for halogenated hydrocarbons, the abbreviation of the compound is described in parentheses after the compound name, but in the present specification, the abbreviation is used instead of the compound name as necessary.

Further, in the present specification, the compound name and the abbreviation of the compound are used without particular notice with respect to the compound in which the Z-form and the E-form which are geometric isomers are present depending on the position of the substituent bonded to the carbon having a double bond. When used, it indicates a Z-form or an E-form, or a mixture of Z-form and E-form in any ratio. When (Z) or (E) is added after the compound name or the abbreviation of the compound, it indicates that it is the Z-form or the E-form of each compound.

[Composition for thermodynamic cycle system]
Thermodynamic cycle system composition of the present embodiment, at least one selected from the HFO-1123, CF ₃ I and hydrofluorocarbons (HFC), HFO-1123 except hydrofluoroolefin (HFO) and hydro carbon (HC) It has a working medium for a thermal cycle (hereinafter, also simply referred to as “working medium”) containing a compound and having a temperature gradient of 7 ° C. or lower.

The composition for a thermodynamic cycle system of the present embodiment has an operating medium having a suppressed temperature gradient, and can be used as an operating medium that can be used in place of, for example, R410A or R407C.

<Operating medium>
Thermodynamic cycle system composition of the present embodiment includes a working medium containing the HFO-1123, CF ₃ I and HFC, at least one compound selected from the HFO and HC other than HFO-1123 as described above.

HFO-1123 used in this embodiment is 1,1,2-trifluoroethylene known as an operating medium. This HFO-1123 has high cycle performance for a thermal cycle, has a low GWP, and is a preferable compound as an operating medium in consideration of the global environment. Table 1 shows the relative cycle performance (relative coefficient of performance and relative refrigerating capacity) of this HFO-1123. This relative cycle performance is a relative comparison with R410A (pseudo-azeotropic mixed refrigerant having a mass ratio of HFC-32 and HFC-125 of 1: 1). In the present specification, the relative coefficient of performance is also referred to as relative COP, and the relative refrigerating capacity is also referred to as relative capacity. The composition for a cycle system of the present embodiment is also considered from the viewpoint of alternatives to R407C (a mixed composition having a mass ratio of 23:25:52 with HFC-32, HFC-125 and HFC-134a) and R134a. Table 1 also shows the values of relative comparison of R407C and R134a with R410A for reference.

_{CF 3} I used in this embodiment can act as an actuating medium and suppress autolysis of HFO-1123. Although the proportion of other components also affects, it is a component that can suppress combustibility when the composition for a thermodynamic cycle system containing a thermodynamic cycle operating medium is released into the air.

The compound used in this embodiment is at least one compound selected from HFOs and HCs other than HFCs and HFO-1123. These compounds can improve the desired properties when used in combination with HFO-1123 and CF _{3 I described above.} Hereinafter, each of these compounds will be described.

(HFC)
The HFC used in this embodiment is preferably selected from the above viewpoint. That is, the HFC to be combined with HFO-1123 and CF ₃ I is appropriately selected from the viewpoint of improving the cycle performance as the working medium and keeping the temperature gradient within an appropriate range. Further, it is preferable that the GWP is appropriately selected from the viewpoint of keeping the GWP within an acceptable range and suppressing flammability when the composition is used for a thermodynamic cycle system.

Specifically, as an HFC having a small effect on the ozone layer and a small effect on global warming, an HFC having 1 to 5 carbon atoms is preferable. The HFC may be linear, branched, or cyclic.

Examples of HFCs include difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane (HFC-125), pentafluoropropane, hexafluoropropane, and heptafluoropropane. , Pentafluoroethane, heptafluorocyclopentane and the like.

Among them, HFCs have little effect on the ozone layer and have excellent refrigeration cycle characteristics, so HFC-32, HFC-161, 1,1-difluoroethane (HFC-152a), 1,1,1-tri Fluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), and HFC-125 are preferred, and HFC. -32, HFC-161, HFC-152a, HFC-134a, and HFC-125 are more preferred, and HFC-32, HFC-134a, and HFC-125 are even more preferred.
One type of HFC may be used alone, or two or more types may be used in combination.

(HFO)
It is preferable that HFO as an optional component other than HFO-1123 is also selected from the same viewpoint as the above HFC. In addition, even if it is other than HFO-1123, if it is HFO, GWP is an order of magnitude lower than that of HFC. Therefore, as an HFO other than HFO-1123 to be combined with HFO-1123, the cycle performance as the operating medium is improved, and the temperature gradient and the discharge temperature difference are kept within an appropriate range, rather than considering GWP. It is preferable to make an appropriate selection with particular attention.

Examples of HFOs other than HFO-1123 include 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,1-difluoroethylene (HFO-1132a), and trans-1,2-difluoroethylene (HFO-1132). (E)), cis-1,2-difluoroethylene (HFO-1132 (Z)), 2-fluoropropene (HFO-1261yf), 1,1,2-trifluoropropene (HFO-1243yc), trans-1 , 2,3,3,3-pentafluoropropene (HFO-1225ye (E)), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye (Z)), trans-1,3 , 3,3-Tetrafluoropropene (HFO-1234ze (E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)), 3,3,3-trifluoropropene (HFO) -1243zf) and the like.

Among them, HFOs other than HFO-1123 have a high critical temperature and are excellent in safety and performance coefficient. Therefore, HFO-1132 (E), HFO-1132 (Z), HFO-1234yf, HFO-1234ze (E), HFO-1234ze (Z), HFO-1243zf are preferable, and HFO-1132 (E), HFO-1132 (Z), HFO-1234yf, HFO-1234ze (E), HFO-1234ze (Z) are more preferable. Preferably, HFO-1234yf is even more preferred. As the HFO other than HFO-1123, one type may be used alone, or two or more types may be used in combination.

(HC)
Examples of HC include propane, propylene, cyclopropane, butane, isobutane, pentane, and isopentane. Among them, propane is preferable as HC because it is excellent in safety and coefficient of performance and can have a low GWP.
One type of HC may be used alone, or two or more types may be used in combination.

The working medium used in the present embodiment contains, _{in addition to HFO-1123 and CF 3} I described above, a compound used in combination with these as an essential component. Hereinafter, the content of each component in the working medium will be described.

When HFC is contained, the content thereof can be arbitrarily selected according to the required characteristics of the working medium. In the case of a working medium containing HFO-1123, CF ₃ I and HFC-125, the content of HFO-1123 is 40 to 60% by mass, _{the content of CF 3} I is 10 to 30% by mass, and the content of HFC-125. Is preferable because the temperature gradient is lowered in the range of 20 to 30% by mass and the relative performance coefficient is improved. Further, from the viewpoint of lowering the higher temperature gradient, content of 50 to 60% by weight of HFO-1123, the content of CF ₃ I 10 to 20 wt%, the content of HFC-125 is 20 to 30 wt% range Is more preferable. HFC-125 is also preferable from the viewpoint of making the obtained working medium incombustible.

In the case of a working medium containing HFO-1123, CF ₃ I and HFC-134a, the content of HFO-1123 is 30 to 60% by mass, _{the content of CF 3} I is 10 to 40% by mass, and the content of HFC-134a. It is preferable to lower the temperature gradient in the range of 20 to 40% by mass. Further, from the viewpoint of increasing the more capable, 40-60 mass% content of HFO-1123, CF ₃ content of I 10 to 30 wt%, the content of HFC-134a is in the range of 20 to 40 wt% More preferred. HFC-134a is also preferable from the viewpoint of making the obtained working medium incombustible.

In the case of a working medium containing HFO-1123, CF ₃ I and HFC-32, the content of HFO-1123 is more than 0 and 60% by mass or less, _{the content of CF 3} I is 10 to 60% by mass, and HFC-32. It is preferable that the temperature gradient is lowered in the range of the content of less than 10 to 90% by mass, and the relative coefficient of performance is improved. When decreasing the GWP is 60 mass% content of more than 0 of HFO-1123 or less, CF ₃ I content of less than 10 wt percent 50 wt% of the content of HFC-32 is more than 10 wt% A range of less than 90% by mass is more preferable. HFC-32 is also preferable from the viewpoint of suppressing the GWP of the obtained working medium to a low level.

In the case of a working medium containing HFO-1123, CF ₃ I and HFC-161, the content of HFO-1123 is 30 to 60% by mass, _{the content of CF 3} I is 20 to 50% by mass, and the content of HFC-161. It is preferable to lower the temperature gradient in the range of 10 to 30% by mass. Further, from the viewpoint of lowering the higher temperature gradient, content of 30 to 60% by weight of HFO-1123, the content of CF ₃ I 20 to 50 wt%, the content of HFC-161 is 20 to 30 wt% range Is more preferable.

When HFC is contained, a plurality of types of HFC may be contained. The content can be arbitrarily selected according to the required characteristics of the working medium. For example, in the case of a working medium containing HFO-1123, CF ₃ I, HFC-125 and HFC-32, the content of HFO-1123 is 10 to 40% by mass, and _{the content of CF 3} I is 30 to 50% by mass. It is preferable to lower the temperature gradient in the range where the content of HFC-125 is 10 to 20% by mass and the content of HFC-32 is 10 to 40% by mass. From the viewpoint of improving the relative capacity, content of 10 to 40% by weight of HFO-1123, the content of CF ₃ I is less than 20 mass% to 40 mass%, the content of HFC-125 10 to 20 The mass% and the content of HFC-32 are preferably in the range of 10 to 40% by mass.

Further, for example, in _{the case of a working medium containing HFO-1123, CF 3} I, HFC-125, HFC-134a and HFC-32, the content of HFO-1123 is 10 to 40% by mass, and _{the content of CF 3} I is high. Temperature gradient in the range of 10 to 30% by mass, HFC-125 content of 5 to 15% by mass, HFC-134a content of 10 to 30% by mass, and HFC-32 content of 10 to 40% by mass. Is preferable. Further, from the viewpoint of lowering the higher temperature gradient, content of 10 to 40% by weight of HFO-1123, CF ₃ content of I 10 mass percent 30 wt% or less, the content of HFC-125 is from 5 to 15 mass %, The content of HFC-134a is 10% by mass or more and less than 30% by mass, and the content of HFC-32 is 10 to 40% by mass, which is more preferable.

When an HFO other than HFO-1123 is contained, the content thereof can be arbitrarily selected according to the required characteristics of the working medium. For example, in the case of a working medium containing HFO-1123, CF ₃ I and HFO-1234yf, the content of HFO-1123 is 10 to 40% by mass, _{the content of CF 3} I is 20 to 80% by mass, and HFO-1234yf. When the content is in the range of 10 to 70% by mass, it is preferable because it can have a sufficient capacity with respect to the relative capacity (R410A ratio) of 0.45 of the 134a refrigerant.
From the viewpoint of lowering the higher temperature gradient, content of 10 to 20% by weight of HFO-1123, CF ₃ content of I 20 to 80 wt%, the content of HFO-1234yf is 10 super 70 mass% of The range is preferred. On the other hand, from the viewpoint of improving the relative capacity, HFO-1123 content of 20 to 40 mass% of, CF ₃ content of 20 to 50 wt% of I, the content of HFO-1234yf is 30 mass percent 60 weight The range of% or less is preferable.

Further, for example, in _{the case of a working medium containing HFO-1123, CF 3} I and HFO-1234ze (E), the content of HFO-1123 is 10 to 20% by mass and _{the content of CF 3} I is 30 to 70% by mass. When the content of HFO-1234ze (E) is in the range of 20 to 60% by mass, it is preferable because it can have a sufficient capacity with respect to the relative capacity (compared to R410A) 0.45 of the 134a refrigerant.
From the viewpoint of improving the relative capacity, 15-20% by weight content of HFO-1123, CF ₃ content of I is 40-50 wt%, the content of HFO-1234ze (E) 30~40 The mass% range is preferred.

Further, for example, in _{the case of a working medium containing HFO-1123, CF 3} I and HFO-1132 (E), the content of HFO-1123 is 10 to 90% by mass and _{the content of CF 3} I is 10 to 40% by mass. When the content of HFO-1132 (E) is in the range of 10 to 80% by mass, it is preferable that it can have a sufficient capacity with respect to the relative capacity (R410A ratio) of the 134a refrigerant of 0.45.
Further, from the viewpoint of further lowering the temperature gradient, the content of HFO-1123 is 10 to 90% by mass, _{the content of CF 3} I is 10 to 20% by mass, and the content of HFO-1132 (E) is 10 to 80% by mass. The range of% or less is preferable. On the other hand, from the viewpoint of improving the relative capacity, content of 20 to 90% by weight of HFO-1123, CF ₃ content of 10 to 30 wt% of I, the content of HFO-1132 (E) is 10 wt% The range of ~ 80% by mass or less is preferable.
HFO-1123 and HFO-1132 (E) are known to undergo an autolysis reaction. From the viewpoint of suppressing the autolysis reaction, the total content of HFO-1123 and HFO-1132 (E) is preferably 60% by mass or less.

Further, for example, in _{the case of a working medium containing HFO-1123, CF 3} I and HFO-1132 (Z), the content of HFO-1123 is 10 to 20% by mass, and _{the content of CF 3} I is 10 to 60% by mass. When the content of HFO-1132 (Z) is in the range of 10 to 80% by mass, it is preferable that it can have a sufficient capacity with respect to the relative capacity (R410A ratio) of the 134a refrigerant of 0.45.
HFO-1123 and HFO-1132 (Z) are known to undergo an autolysis reaction. From the viewpoint of suppressing the autolysis reaction, the total content of HFO-1123 and HFO-1132 (Z) is preferably 60% by mass or less.

Further, for example, in _{the case of a working medium containing HFO-1123, CF 3} I, HFC-32 and HFO-1132 (E), the content of HFO-1123 is 10 to 80% by mass, and _{the content of CF 3} I is 10. If the content is in the range of ~ 40% by mass, the content of HFC-32 is 10 to 30% by mass, and the content of HFO-1132 (E) is in the range of 10 to 70% by mass, the relative capacity of the 134a refrigerant (compared to R410A) is 0. It is preferable that it has a sufficient ability with respect to 45.
From the viewpoint of lowering the higher temperature gradient, content of 10 to 80% by weight of HFO-1123, CF ₃ content of 10 to 30 wt% of I, the content of HFC-32 is 10 to 30 mass%, HFO The content of -1132 (E) is preferably in the range of 10 to 70% by mass or less. On the other hand, from the viewpoint of improving the relative ability, the content of HFO-1123 is 10 to 80% by mass, _{the content of CF 3} I is 10 to 30% by mass, and the content of HFO-1132 (E) is 10% by mass. The range of ~ 60% by mass or less is preferable.
HFO-1123 and HFO-1132 (E) are known to undergo an autolysis reaction. From the viewpoint of suppressing the autolysis reaction, the total content of HFO-1123 and HFO-1132 (E) is preferably 60% by mass or less.

Further, for example, in _{the case of a working medium containing HFO-1123, CF 3} I, HFO-1234yf and HFO-1132 (E), the content of HFO-1123 is 10 to 80% by mass, and _{the content of CF 3} I is 10. When the content is in the range of ~ 40% by mass and the content of HFO-1132 (E) is in the range of 10 to 80% by mass, it is preferable that the relative capacity (compared to R410A) of the 134a refrigerant is 0.45. ..
Further, from the viewpoint of further lowering the temperature gradient, the content of HFO-1123 is 10 to 80% by mass, _{the content of CF 3} I is 10 to 20% by mass, and the content of HFO-1132 (E) is 10 to 80% by mass. The range of% or less is preferable. On the other hand, from the viewpoint of improving the relative ability, the content of HFO-1123 is 10 to 80% by mass, _{the content of CF 3} I is 10 to 30% by mass, and the content of HFO-1132 (E) is 10% by mass. The range of ~ 80% by mass or less is preferable.
HFO-1123 and HFO-1132 (E) are known to undergo an autolysis reaction. From the viewpoint of suppressing the autolysis reaction, the total content of HFO-1123 and HFO-1132 (E) is preferably 60% by mass or less.

Further, for example, in _{the case of a working medium containing HFO-1123, CF 3} I, HFO-1132 (E) and HFO-1132 (Z), the content of HFO-1123 is 10 to 70% by mass, and _{the content of CF 3} I is contained. If the amount is in the range of 10 to 30% by mass, the content of HFO-1132 (E) is 10 to 70% by mass, and the content of HFO-1132 (Z) is in the range of 10 to 20% by mass, the relative capacity of the 134a refrigerant It is preferable because it can have sufficient capacity with respect to 0.45 (compared to R410A).
Further, from the viewpoint of further lowering the temperature gradient, the content of HFO-1123 is 10 to 70% by mass, _{the content of CF 3} I is 10 to 20% by mass, and the content of HFO-1132 (E) is 10 to 70% by mass. %, The content ratio of HFO-1132 (Z) is preferably in the range of less than 10 to 20% by mass.
HFO-1123, HFO-1132 (E) and HFO-1132 (Z) are known to undergo autolysis reactions. From the viewpoint of suppressing the autolysis reaction, the total content of HFO-1123, HFO-1132 (E) and HFO-1132 (Z) is preferably 60% by mass or less.

When HC is contained as a compound, the content thereof can be arbitrarily selected according to the required characteristics of the working medium. For example, in the case of a working medium containing HFO-1123, CF ₃ I and propane, the content of HFO-1123 is 40 to 60% by mass, _{the content of CF 3} I is 10 to 40% by mass, and the content of propane is 15. It is preferable to lower the temperature gradient in the range of ~ 30% by mass. Further, propane is preferable because it can suppress the GWP of the obtained working medium to a low level. Further, from the viewpoint of lowering the higher temperature gradient, content of 40 to 60% by weight of HFO-1123, CF ₃ I content of 10 to 35 mass% of the content of propane in the range of 20 to 30 wt% and more preferable.

(Other optional ingredients)
The working medium used in the composition for the thermodynamic cycle system of the present embodiment may further contain other optional components such as chlorofluoroolefin (CFO) and hydrochlorofluoroolefin (HCFO). As the other optional component, a component having a small effect on the ozone layer and a small effect on global warming is preferable as long as the effect of the present invention is not impaired.

Examples of the CFO include chlorofluoropropene and chlorofluoroethylene. CFOs include 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 1 , 3-Dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb), 1,2-dichloro-1,2-difluoroethylene (CFO-1112) are preferred.
One type of CFO may be used alone, or two or more types may be used in combination.

When the working medium contains CFO, the content thereof is preferably less than 10% by mass, more preferably 1 to 8% by mass, still more preferably 2 to 5% by mass with respect to 100% by mass of the working medium. When the CFO content is at least the lower limit, it is easy to suppress the flammability of the working medium. When the CFO content is not more than the upper limit, good cycle performance can be easily obtained.

Examples of HCFO include hydrochlorofluoropropene and hydrochlorofluoroethylene. The HCFOs include 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) and 1-chloro because it is easy to suppress the flammability of the working medium without significantly deteriorating the cycle performance of the working medium. -1,2-Difluoroethylene (HCFO-1122) is preferred.
One type of HCFO may be used alone, or two or more types may be used in combination.

When the working medium contains HCFO, the content of HCFO in 100% by mass of the working medium is preferably less than 10% by mass, more preferably 1 to 8% by mass, still more preferably 2 to 5% by mass. When the content of HCFO is at least the lower limit value, it is easy to suppress the combustibility of the working medium. When the content of HCFO is not more than the upper limit value, good cycle performance can be easily obtained.

When the working medium used in the composition for a thermodynamic cycle system of the present invention contains other optional components as described above, the total content of the other optional components in the working medium is 10% by mass with respect to 100% by mass of the working medium. It is preferably less than%, more preferably 8% by mass or less, still more preferably 5% by mass or less.

<Temperature gradient>
The temperature gradient is an index for measuring the difference in composition between the liquid phase and the gas phase in the working medium of the mixture. A temperature gradient is defined as the property of evaporation in a heat exchanger, eg, an evaporator, or condensation in a condenser, with different start and finish temperatures. In the azeotropic mixing medium, the temperature gradient is 0, and in a pseudo azeotropic mixture such as R410A, the temperature gradient is extremely close to 0.

If the temperature gradient is large, for example, the inlet temperature in the evaporator decreases, which increases the possibility of frost formation, which is a problem. Further, in a heat cycle system, in order to improve heat exchange efficiency, it is common to make the operating medium flowing through the heat exchanger and a heat source fluid such as water or air countercurrent, and in a stable operation state, the operation medium is countercurrent. Since the temperature difference between the heat source fluids is small, it is difficult to obtain an energy-efficient heat cycle system in the case of a non-cobo-boiling mixed medium having a large temperature gradient. Therefore, when the mixture is used as the working medium, a working medium having an appropriate temperature gradient is desired.

Further, the non-azeotropic mixed medium has a problem that the composition changes when the pressure vessel is filled into the refrigerating and air-conditioning equipment. Further, when a refrigerant leaks from the refrigerating and air-conditioning equipment, the refrigerant composition in the refrigerating and air-conditioning equipment is extremely likely to change, and it is difficult to restore the refrigerant composition to the initial state. On the other hand, the above problem can be avoided if the azeotropic or pseudo azeotropic mixed medium is used.

Therefore, the composition for a thermal cycle system of the present embodiment has a temperature gradient of 7 ° C. or lower, more preferably 6 ° C. or lower, further preferably 5 ° C. or lower, and particularly preferably 3 ° C. or lower.

<Global Warming Potential (GWP)>
In this embodiment, GWP is used as an index for measuring the influence of the working medium on global warming. In this specification, GWP is the 100-year value of the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (2013) unless otherwise specified. The GWP in the mixture is a weighted average based on the composition mass.

The global warming potential (100 years) of HFO-1123 contained in the working medium according to the present embodiment is 1 as a value measured according to the IPCC Fifth Assessment Report.

Further, R410A (1: 1 (mass) composition of HFC-125 and HFC-32), which is to be replaced by the working medium according to the present embodiment, has an extremely high GWP of 1924 and contains R410A. The GWP is also high for the two types of HFCs and other typical HFCs, such as HFC-134a, as shown in Table 2 below. The R407C (23:25:52 (mass) composition with HFC-32, HFC-125 and HFC-134a), which is to be replaced by the working medium according to the present embodiment and has excellent cycle performance, also has an extremely high GWP of 1624. ..

Since HFO-1123 has a very small GWP as described above, for example, in order to improve cycle performance and the like, when obtaining a mixed composition in combination with an HFC having a high cycle capacity and a high GWP, it is compared with other HFOs. Therefore, it is advantageous in that the cycle performance can be improved while keeping the GWP low. In this embodiment, it also contains _{CF 3} I, which can stabilize HFO-1123.

The working medium used in this embodiment preferably has a GWP of 1000 or less, more preferably 750 or less, further preferably 675 or less, further preferably 500 or less, further preferably 300 or less, more preferably 250 or less, and particularly preferably 150 or less. preferable.

<Cycle performance>
Here, as the properties required when applying the working medium to the thermal cycle, the cycle performance is the coefficient of performance (also referred to as "COP" in the present specification) and the ability ("Q" in the present specification). Also called.) Can be evaluated. If the thermodynamic cycle system is a refrigeration cycle system, the capacity is the refrigeration capacity. In addition to the above cycle performance, the evaluation items when the working medium is applied to the refrigeration cycle system further include the temperature gradient, the compressor discharge gas temperature, and the compressor discharge pressure. Specifically, using the reference refrigeration cycle of the temperature conditions shown below, for example, each item is measured by the method described later, and the relative value is set to a relative value based on the value of R410A as an alternative target except for the temperature gradient. Convert and evaluate. The evaluation items will be specifically described below.

(Temperature condition of standard refrigeration cycle)
Evaporation temperature: 10 ° C (however, in the case of a non-azeotropic mixture, the average temperature of the evaporation start temperature and the evaporation completion temperature)
Condensation completion temperature; 45 ° C. (However, in the case of a non-azeotropic mixture, the average temperature of the condensation start temperature and the condensation completion temperature)
Supercooling degree (SC); 10 ° C
Superheat (SH); 10 ° C
Compressor efficiency; 0.7

<Relative coefficient of performance>
The coefficient of performance is the power (kW) consumed to obtain the output (kW), which is the value obtained by dividing the output (kW), and corresponds to the energy consumption efficiency. The higher the coefficient of performance, the larger the output can be obtained with less input. The relative coefficient of performance for R410A can be calculated by the following equation (1). In addition, in formula (1), the sample shows the working medium to be evaluated relative.

<Relative refrigeration capacity>
Refrigeration capacity is the output in a refrigeration cycle system. The relative refrigerating capacity for R410A can be calculated by the following formula (2). In addition, in formula (2), the sample shows the working medium to be evaluated relative to each other.

<Compressor discharge pressure difference>
From the sample i.e. the compressor discharge gas pressure of the working medium to be relative evaluation (Px), to assess the value obtained by subtracting the compressor discharge gas pressure _{R410A (P R410A) (PΔ)} . The compressor discharge gas pressure in the refrigeration cycle (hereinafter, also referred to as “discharge pressure”) is the maximum pressure in the refrigeration cycle. A low discharge pressure is preferable because it affects the design pressure of the compressor. In order to replace R410A, the discharge pressure must be a pressure that can be tolerated by the thermodynamic cycle system components operating by R410A, even if the discharge pressure is lower or higher than the discharge pressure of R410A.

<Compressor discharge gas temperature difference>
From the sample i.e. the compressor discharge gas temperature of the working medium to be relative evaluation (Tx), to assess the value obtained by subtracting the compressor discharge gas temperature of _{R410A (T R410A) (TΔ)} . The compressor discharge gas temperature in the refrigeration cycle (hereinafter, also referred to as “discharge temperature”) is the maximum temperature in the refrigeration cycle. A low discharge temperature is preferable because it affects the heat resistance of the material constituting the compressor, the refrigerating machine oil normally contained in the composition for the thermal cycle system other than the working medium, and the polymer material. In order to replace R410A, even if the discharge temperature is lower or higher than the discharge temperature of R410A, it is necessary that the temperature is acceptable to the thermodynamic cycle system constituent equipment operated by R410A.

When the working medium used in this embodiment is a substitute for R410A, the relative refrigerating capacity RQ _R410A is preferably 0.70 to 1.50, more preferably 0.90 to 1.50, and 1.00. ~ 1.50 is particularly preferable. In the case of R407C substitution, the relative ability may be evaluated by using the denominators of the above formulas (1) and (2) as the coefficient of performance and refrigerating ability for R407C instead of R410A.

Further, the working medium used in this embodiment can be used not only as a substitute for R410A but also as a substitute for R134a, particularly when it contains an HFO other than HFO-1123. In that case, the relative refrigerating capacity RQ _R410A is preferably 0.45 to 1.50, more preferably 0.50 to 1.50, and particularly preferably 0.55 to 1.50.

The relative coefficient of performance RCAP _R410A is preferably 0.85 to 1.20, more preferably 0.99 to 1.20, and particularly preferably 0.95 to 1.20.

The discharge pressure difference PΔ is preferably 500 or less, more preferably 100 or less, and particularly preferably 0 or less.

The discharge temperature difference TΔ is preferably 30 ° C. or lower, more preferably 20 ° C. or lower, and particularly preferably 10 ° C. or lower.

As the refrigeration cycle system used for evaluating the above characteristics, for example, the refrigeration cycle system whose schematic configuration diagram is shown in FIG. 1 can be used. Hereinafter, a method for evaluating the cycle performance, the temperature gradient, the compressor discharge gas temperature (Tx), and the compressor discharge pressure (Px) will be described using the refrigeration cycle system shown in FIG.

In the refrigeration cycle system 10 shown in FIG. 1, the compressor 11 that compresses the working medium steam A to obtain the high-temperature and high-pressure working medium steam B and the working medium steam B discharged from the compressor 11 are cooled and liquefied. A condenser 12 serving as a low-temperature and high-pressure working medium C, an expansion valve 13 that expands the working medium C discharged from the condenser 12 to form a low-temperature and low-pressure working medium D, and a working medium D discharged from the expansion valve 13. A schematic configuration including an evaporator 14 for heating a high-temperature and low-pressure working medium vapor A, a pump 15 for supplying a load fluid E to the evaporator 14, and a pump 16 for supplying a fluid F to a condenser 12. It is a system to be done.

In the refrigeration cycle system 10, the following cycles (i) to (iv) are repeated.
(I) The working medium steam A discharged from the evaporator 14 is compressed by the compressor 11 to obtain a high temperature and high pressure working medium steam B (hereinafter referred to as "AB process").
(Ii) The working medium steam B discharged from the compressor 11 is cooled by the fluid F in the condenser 12 and liquefied to obtain a low-temperature and high-pressure working medium C. At this time, the fluid F is heated to become the fluid F'and is discharged from the condenser 12 (hereinafter, referred to as "BC process").
(Iii) The working medium C discharged from the condenser 12 is expanded by the expansion valve 13 to obtain a low-temperature low-pressure working medium D (hereinafter referred to as “CD process”).
(Iv) The working medium D discharged from the expansion valve 13 is heated by the load fluid E in the evaporator 14 to obtain high temperature and low pressure working medium steam A. At this time, the load fluid E is cooled to become the load fluid E'and is discharged from the evaporator 14 (hereinafter, referred to as "DA process").

The refrigeration cycle system 10 is a cycle system including heat insulation / isentropic change, isentropic change, and isobaric change. When the state change of the working medium is described on the pressure-enthalpy line (curve) diagram shown in FIG. 2, it can be represented as a trapezoid having A, B, C, and D as vertices.

The AB process is a process in which adiabatic compression is performed by the compressor 11 to convert the high-temperature and low-pressure working medium steam A into the high-temperature and high-pressure working medium steam B, which is shown by the AB line in FIG. As will be described later, the working medium steam A is introduced into the compressor 11 in a superheated state, and the obtained working medium steam B is also a superheated steam.
The compressor discharge gas temperature (discharge temperature) is the temperature (Tx) in the state B in FIG. 2, which is the maximum temperature in the refrigeration cycle. The compressor discharge pressure (discharge pressure) is the pressure (Px) in the state B in FIG. 2, which is the maximum pressure in the refrigeration cycle. Since the BC process is isobaric cooling, the discharge pressure shows the same value as the condensation pressure. Therefore, in FIG. 2, the condensation pressure is shown as Px for convenience.

The BC process is a process in which the condenser 12 is used for isobaric cooling to convert the high-temperature and high-pressure working medium steam B into the low-temperature and high-pressure working medium C, which is shown by the BC line in FIG. The pressure at this time is the condensation pressure. Pressure - an intersection T ₁ of the high enthalpy side condensing temperature of the intersection of the enthalpy and BC line, the low enthalpy side intersection T ₂ is the condensation boiling temperature. Here, the temperature gradient when the working medium is a non-azeotropic mixed medium is shown as the difference between _{T 1} and T _2.

The CD process is a process in which the expansion valve 13 performs isoenthalpy expansion to use the low-temperature and high-pressure operating medium C as the low-temperature and low-pressure operating medium D, which is shown by the CD line in FIG. Incidentally, if Shimese the temperature in the working medium C of low temperature and high pressure at _{T 3, T} 2 -T ₃ is (i) ~ supercooling degree of the working medium in the cycle of (iv) (SC).

The DA process is a process of performing isobaric heating with the evaporator 14 to return the low-temperature low-pressure working medium D to the high-temperature low-pressure working medium steam A, which is shown by the DA line in FIG. The pressure at this time is the vapor pressure. Pressure - intersection T ₆ of the high enthalpy side of the intersection of the enthalpy and DA line is evaporating temperature. If Shimese the temperature of the working medium vapor A in _{T 7, T 7} -T ₆ is (i) ~ superheat of the working medium in the cycle of (iv) (SH). Note that T ₄ indicates the temperature of the working medium D.

The Q and COP of the working medium are in each state of A (after evaporation, high temperature and low pressure), B (after compression, high temperature and high pressure), C (after condensation, low temperature and high pressure), and D (after expansion, low temperature and low pressure). each _{enthalpy, h a, h B, h} C, the use of _{h D,} the following equation (11), obtained respectively from (12). There shall be no loss due to equipment efficiency and no pressure loss in piping and heat exchangers.

The thermodynamic properties required to calculate the cycle performance of the working medium can be calculated based on the generalized equation of state (Soave-Redlich-Kwong equation) based on the corresponding state principle and various thermodynamic relational expressions. If the characteristic value is not available, the calculation is performed using the estimation method based on the atomic group contribution method.
Q = h _A −h _D … (11)
COP = Q / compression work = (h _A- h _D ) / (h _B- h _A ) ... (12)

The Q indicated by (h _A- h _D ) above corresponds to the output (kW) of the refrigeration cycle and is required to operate the compression work indicated by _{(h B-} h _{A), for example, the compressor.} The amount of electric power corresponds to the consumed power (kW). In addition, Q means the ability to freeze the loaded fluid, and the higher the Q, the more work can be done in the same system. In other words, when it has a large Q, it means that the desired performance can be obtained with a small amount of working medium, and the system can be miniaturized.

As the heat cycle system to which the composition for the heat cycle system of the present embodiment is applied, a heat cycle system using a heat exchanger such as a condenser or an evaporator is used without particular limitation. In a thermal cycle system, for example, a refrigeration cycle, a working medium of gas is compressed by a compressor and cooled by a condenser to produce a high-pressure liquid, the pressure is lowered by an expansion valve, and the vapor is vaporized by low-temperature vaporization by an evaporator. It has a mechanism to remove heat with heat.

The composition for a thermodynamic cycle system of the present invention contains, in addition to the above-mentioned working medium, refrigerating machine oil in the same manner as that of a composition for a normal thermodynamic cycle system. In addition to these, the composition for a thermodynamic cycle system including the working medium and the refrigerating machine oil may further contain known additives such as a stabilizer and a leak detection substance.

<Non-flammable>
The composition for the thermodynamic cycle system of the present embodiment is preferably nonflammable. Whether or not it is nonflammable can be evaluated by the following flammability test on the contained working medium.
The flammability evaluation can be carried out using the equipment specified in ASTME-681. Each working medium is mixed so as to have a predetermined ratio to obtain a working medium to be evaluated, and the obtained working medium is mixed with air at a predetermined ratio. For mixing with air, the working medium is mixed with air at a ratio of 1% by mass between 10 and 90% by mass, and the combustibility when the equilibrium state is reached is evaluated.

After vacuum evacuating the inside of a flask having an internal volume of 12 liters installed in a constant temperature bath whose temperature is controlled to 25 ° C., each working medium mixed with air at the above ratio is sealed to atmospheric pressure. Then, in the gas phase near the center of the flask, discharge ignition is performed at 15 kV and 30 mA for 0.4 seconds, and then the spread of the flame is visually confirmed. When the angle of the upward flame spread is 90 ° or more, it is judged to be combustible, and when it is less than 90 °, it is judged to be nonflammable.

<Refrigerator oil>
As the refrigerating machine oil, a known refrigerating machine oil used in a composition for a thermal cycle system can be adopted without particular limitation together with a working medium conventionally made of a halogenated hydrocarbon. Specific examples of the refrigerating machine oil include oxygen-containing synthetic oils (ester-based refrigerating machine oils, ether-based refrigerating machine oils, etc.), fluorine-based refrigerating machine oils, mineral-based refrigerating machine oils, hydrocarbon-based synthetic oils, and the like.

Examples of the ester-based refrigerating machine oil include dibasic acid ester oil, polyol ester oil, complex ester oil, and polyol carbonate oil.

The dibasic acid ester oil includes dibasic acids having 5 to 10 carbon atoms (glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, etc.) and carbon atoms having a linear or branched alkyl group. Esters with 1 to 15 monohydric alcohols (methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, etc.) are preferred. Specific examples thereof include ditridecyl glutarate, di (2-ethylhexyl) adipate, diisodecyl adipate, ditridecyl adipate, and di (3-ethylhexyl) sebacate.

Examples of the polyol ester oil include diols (ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 1,5-pentadiol, neopentyl glycol, 1,7- Heptanediol, 1,12-dodecanediol, etc.) or polyols having 3 to 20 hydroxyl groups (trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, glycerin, sorbitol, sorbitan, sorbitol glycerin condensate, etc.) Fatty acids with 6 to 20 carbon atoms (hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, eicosanoic acid, oleic acid and other linear or branched fatty acids, or α carbon atoms are 4 Esters with grades (so-called neoacids, etc.) are preferable.
In addition, these polyol ester oils may have a free hydroxyl group.

As the polyol ester oil, esters of hindered alcohols (neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, etc.) (trimethylolpropane tripleragonate, pentaerythritol 2-ethylhexanoate, etc.) , Pentaerythritol tetrapelargonate, etc.) is preferable.

Complex ester oils are esters of fatty acids and dibasic acids with monohydric alcohols and polyols. As the fatty acid, dibasic acid, monohydric alcohol, and polyol, the same ones as described above can be used.

The polyol carbonic acid ester oil is an ester of carbonic acid and a polyol.
Examples of the polyol include the same diol as described above and the same polyol as described above. Further, the polyol carbonate oil may be a ring-opening polymer of cyclic alkylene carbonate.

Examples of the ether-based refrigerating machine oil include polyvinyl ether oil and polyoxyalkylene oil.

Examples of the polyvinyl ether oil include those obtained by polymerizing a vinyl ether monomer such as alkyl vinyl ether, and copolymers obtained by copolymerizing a vinyl ether monomer and a hydrocarbon monomer having an olefinic double bond.

As the vinyl ether monomer, one type may be used alone, or two or more types may be used in combination.

Hydrocarbon monomers having an olefinic double bond include ethylene, propylene, various butenes, various pentenes, various hexenes, various heptenes, various octenes, diisobutylene, triisobutylene, styrene, α-methylstyrene, various alkyl-substituted styrenes, etc. Can be mentioned. As the hydrocarbon monomer having an olefinic double bond, one type may be used alone, or two or more types may be used in combination.

The polyvinyl ether copolymer may be either a block or a random copolymer. As the polyvinyl ether oil, one type may be used alone, or two or more types may be used in combination.

Examples of the polyoxyalkylene oil include polyoxyalkylene monool, polyoxyalkylene polyol, alkyl ether products of polyoxyalkylene monool and polyoxyalkylene polyol, and esterified products of polyoxyalkylene monool and polyoxyalkylene polyol. ..

For polyoxyalkylene monool and polyoxyalkylene polyol, ring-opening of an alkylene oxide having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, etc.) as an initiator such as water or a hydroxyl group-containing compound in the presence of a catalyst such as alkali hydroxide. Examples thereof include those obtained by a method of addition polymerization or the like. Further, the oxyalkylene unit in the polyalkylene chain may be the same in one molecule, or may contain two or more kinds of oxyalkylene units. It is preferable that at least oxypropylene unit is contained in one molecule.

Examples of the initiator used in the reaction include water, monohydric alcohols such as methanol and butanol, and polyhydric alcohols such as ethylene glycol, propylene glycol, pentaerythritol, and glycerol.

As the polyoxyalkylene oil, alkyl ethers or esters of polyoxyalkylene monools and polyoxyalkylene polyols are preferable. Further, as the polyoxyalkylene polyol, polyoxyalkylene glycol is preferable. In particular, an alkyl ether product of polyoxyalkylene glycol, which is called polyglycol oil, in which the terminal hydroxyl group of polyoxyalkylene glycol is capped with an alkyl group such as a methyl group is preferable.

Examples of the fluorine-based refrigerating machine oil include compounds in which the hydrogen atom of synthetic oil (mineral oil, polyα-olefin, alkylbenzene, alkylnaphthalene, etc., which will be described later) is replaced with a fluorine atom, perfluoropolyether oil, fluorinated silicone oil, and the like. ..

As the mineral-based refrigerating machine oil, the refining machine oil distillate obtained by atmospheric distillation or vacuum distillation of crude oil is refined (solvent desorption, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrogenation). Examples thereof include paraffin-based mineral oil and naphthen-based mineral oil refined by appropriately combining (refining, white clay treatment, etc.).

Examples of the hydrocarbon-based synthetic oil include polyα-olefins, alkylbenzenes, and alkylnaphthalene.

As the refrigerating machine oil, one type may be used alone, or two or more types may be used in combination.
The refrigerating machine oil is preferably one or more selected from polyol ester oil, polyvinyl ether oil and polyglycol oil from the viewpoint of compatibility with the working medium.

The content of the refrigerating machine oil in the composition for a thermodynamic cycle system may be a range that does not significantly reduce the effect of the present invention, and is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the working medium, and is preferably 20 to 50 parts by mass. The portion is more preferable.

<Other optional ingredients>
Stabilizers optionally contained in thermodynamic cycle system compositions are components that improve the stability of the working medium against heat and oxidation. The stabilizer is not particularly limited to a known stabilizer used in a thermal cycle system, for example, an oxidation resistance improver, a heat resistance improver, a metal deactivator, etc., together with a working medium conventionally composed of a halogenated hydrocarbon. Can be adopted.

Examples of the oxidation resistance improver and the heat resistance improver include N, N'-diphenylphenylenediamine, p-octyldiphenylamine, p, p'-dioctyldiphenylamine, N-phenyl-1-naphthylamine, and N-phenyl-2-naphthylamine. , N- (p-dodecyl) phenyl-2-naphthylamine, di-1-naphthylamine, di-2-naphthylamine, N-alkylphenothylamine, 6- (t-butyl) phenol, 2,6-di- (t-butyl) ) Phenol, 4-methyl-2,6-di- (t-butyl) phenol, 4,4'-methylenebis (2,6-di-t-butylphenol) and the like. As the oxidation resistance improver and the heat resistance improver, one type may be used alone, or two or more types may be used in combination.

Examples of the metal deactivator include imidazole, benzimidazole, 2-mercaptobenzthiazole, 2,5-dimethylcaptothiazylazole, salicylidine-propylenediamine, pyrazole, benzotriazole, tortriazole, 2-methylbenzamidazole, 3,5-. Dimethylpyrazole, methylenebis-benzotriazole, organic acids or esters thereof, primary, secondary or tertiary aliphatic amines, amine salts of organic or inorganic acids, heterocyclic nitrogen-containing compounds, alkyl acid phosphates Amine salts of, or derivatives thereof and the like can be mentioned.

The content of the stabilizer in the composition for a thermodynamic cycle system may be a range that does not significantly reduce the effect of the present invention, and is preferably 5 parts by mass or less, preferably 1 part by mass or less, based on 100 parts by mass of the working medium. More preferred.

Examples of the leak detection substance optionally contained in the composition for a thermal cycle system include an ultraviolet fluorescent dye, an odor gas, an odor masking agent, and the like.

Examples of the ultraviolet fluorescent dye are described in US Pat. No. 4,249,412, JP-A-10-502737, JP-A-2007-511645, App. Examples thereof include known ultraviolet fluorescent dyes used in thermal cycle systems, as well as working media conventionally made of halogenated hydrocarbons.

Examples of the odor masking agent include known fragrances used in thermal cycle systems, as well as working media conventionally made of halogenated hydrocarbons, such as those described in Japanese Patent Publication No. 2008-500437 and Japanese Patent Publication No. 2008-531836. Can be mentioned.

When a leak-detecting substance is used, a solubilizer that improves the solubility of the leak-detecting substance in the working medium may be used.

Examples of the solubilizer include those described in JP-A-2007-511645, JP-A-2008-500437, and JP-A-2008-531836.

The content of the leak-detecting substance in the composition for a thermal cycle system may be a range that does not significantly reduce the effect of the present invention, and is preferably 2 parts by mass or less, preferably 0.5 mass by mass, based on 100 parts by mass of the working medium. Less than a part is more preferable.

[Thermodynamic cycle system]
The thermodynamic cycle system of the present embodiment is a system using the composition for the thermodynamic cycle system of the present embodiment. The heat cycle system of the present embodiment may be a heat pump system that utilizes the heat obtained from the condenser, or may be a refrigeration cycle system that utilizes the cold heat obtained from the evaporator.

Specific examples of the heat cycle system of the present embodiment include refrigerating / refrigerating equipment, air conditioning equipment, power generation systems, heat transport equipment, and secondary coolers. Among them, the thermodynamic cycle system of the present invention is preferably used as an air conditioner that is often installed outdoors because it can stably and safely exhibit thermodynamic cycle performance even in a higher temperature operating environment. It is also preferable that the thermodynamic cycle system of the present embodiment is used as a freezing / refrigerating device.

Specific examples of the air conditioner include room air conditioners, package air conditioners (store package air conditioners, building package air conditioners, equipment package air conditioners, etc.), gas engine heat pumps, train air conditioners, automobile air conditioners, and the like.

Specific examples of the freezing / refrigerating equipment include showcases (built-in showcases, separate showcases, etc.), commercial freezers / refrigerators, vending machines, ice makers, and the like.

As the power generation system, a power generation system using the Rankine cycle system is preferable.
As a power generation system, specifically, the working medium is heated by geothermal energy, solar heat, waste heat in a medium to high temperature range of about 50 to 200 ° C., etc. in an evaporator, and the working medium that has become steam in a high temperature and high pressure state is expanded. An example is a system in which an adiabatic expansion is performed by a machine and a generator is driven by the work generated by the adiabatic expansion to generate electricity.

Further, the thermodynamic cycle system of the present embodiment may be a heat transport device. As the heat transport device, a latent heat transport device is preferable.

Examples of the latent heat transport device include a heat pipe and a two-phase sealed heat siphon device that carry out latent heat transport by utilizing phenomena such as evaporation, boiling, and condensation of the working medium enclosed in the device. Heat pipes are applied to relatively small cooling devices such as cooling devices for heat generating parts of semiconductor elements and electronic devices. Since the two-phase sealed heat siphon does not require a wig and has a simple structure, it is widely used for gas-gas heat exchangers, promotion of snow melting on roads, prevention of freezing, and the like.

When operating the thermodynamic cycle system, it is preferable to provide means for suppressing such mixing in order to avoid the occurrence of problems due to the mixing of water and the mixing of non-condensable gas such as oxygen.

Moisture in the thermodynamic cycle system can cause problems, especially when used at low temperatures. For example, problems such as freezing in the capillary tube, hydrolysis of the working medium and refrigerating machine oil, material deterioration due to the acid component generated in the cycle, and generation of contaminants occur. In particular, when the refrigerating machine oil is polyglycol oil, polyol ester oil, etc., the hygroscopicity is extremely high, a hydrolysis reaction is likely to occur, the characteristics of the refrigerating machine oil are deteriorated, and the long-term reliability of the compressor is impaired. It is a big cause. Therefore, in order to suppress the hydrolysis of refrigerating machine oil, it is necessary to control the water concentration in the thermal cycle system.

Examples of the method for controlling the water concentration in the thermal cycle system include a method using a water removing means such as a desiccant (silica gel, activated alumina, zeolite, etc.). The desiccant is preferably in contact with a liquid thermodynamic cycle system composition in terms of dehydration efficiency. For example, it is preferable to place a desiccant at the outlet of the condenser 12 or the inlet of the evaporator 14 to bring it into contact with the composition for a thermodynamic cycle system.

As the desiccant, a zeolite-based desiccant is preferable from the viewpoint of chemical reactivity between the desiccant and the composition for a thermal cycle system and the hygroscopic ability of the desiccant.

In the thermodynamic cycle system of the present invention described above, by using the working medium of the present invention, it is possible to obtain practically sufficient cycle performance while suppressing the influence on global warming with high safety. There is almost no problem with the temperature gradient.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Examples 1-1 to 1-11]
In Examples 1-1 to 1-11, a working medium composed of HFO-1123 and CF ₃ I and mixed at the ratios shown in Table 3 was prepared. Table 3 shows the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

The results of measuring and calculating the temperature gradient, discharge temperature difference and refrigeration cycle performance (relative refrigerating capacity and relative coefficient of performance) for the working medium containing each compound shown in Table 4 below are as follows. be.

[Example 1-12-1-50]
In Examples 1-12 to 1-50, _{a working medium was prepared in which HFO-1123 and CF 3} I were mixed with HFO-1132 (E) at the ratios shown in Table 5. Table 5 shows the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Example 1-511-89]
In the example 1-51～1-89, in addition to HFO-1123 and CF ₃ I, and HFO-1132 a (Z) to prepare a working medium in a mixing ratio shown in Table 6. Table 6 shows the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Examples 1-90 to 1-134]
In Examples 1-90 to 1-134, in addition to HFO-1123 and CF ₃ I, HFO-1132 (E) and HFO-1132 (Z) were mixed at the ratios shown in Table 7 to prepare working media. Table 7 shows the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Examples 2-1 to 2-32]
In the example 2-1～2-32, in addition to HFO-1123 and CF ₃ I, to prepare a working medium of a mixture of HFC-125 at a ratio shown in Table 8. Table 8 shows the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Examples 3-1 to 2-327]
In the example 3-1～3-27, in addition to HFO-1123 and CF ₃ I, to prepare a working medium in a mixing ratio shown in Table 9 the HFC-134a. Table 9 shows the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Examples 4-1 to 4-39]
In the example 4-1～4-39, in addition to HFO-1123 and CF ₃ I, to prepare a working medium of a mixture of HFC-32 at a ratio shown in Table 10. Table 10 shows the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Examples 4-40 to 4-120]
In the example 4-40～4-120, in addition to HFO-1123 and CF ₃ I, and HFC-32 and HFO-1132 (E) is to prepare a working medium in a mixing ratio shown in Table 11 and Table 12. Tables 11 and 12 show the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Examples 5-1 to 5-34]
In Examples 5-1 to 5-34, _{a working medium was prepared in which HFO-1123 and CF 3} I were mixed with HFO-1234yf at the ratios shown in Table 13. Table 13 shows the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Example 5-35-5-140]
In Examples 5-35-5-140, a working medium was prepared in which HFO-1123 and CF ₃ I were mixed with HFO-1234yf and HFO-1132 (E) in the proportions shown in Tables 14-16. Tables 14 to 16 show the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Examples 6-1 to 6-25]
In Examples 6-1 to 6-25, _{a working medium was prepared in which HFO-1123 and CF 3} I were mixed with HFO-1234ze (E) at the ratios shown in Table 17. Table 17 shows the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Examples 7-1 to 7-49]
In Examples 7-1 to 7-49, _{a working medium was prepared by mixing HFO-1123 and CF 3} I with propane in the proportions shown in Table 18. Table 18 shows the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Examples 8-1 to 8-49]
In Examples 8-1 to 8-49, a working medium was prepared in which HFC-161 was mixed in the ratio shown in Table 19 in addition _{to HFO-1123 and CF 3 I.} Table 19 shows the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Example 9-1 to 9-18]
In Examples 9-1 to 9-18, a working medium was prepared in which HFC-125 and HFC-32 were mixed in the ratio shown in Table 20 in addition _{to HFO-1123 and CF 3 I.} Table 20 shows the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Example 10-1 to 10-12]
In the example 10-1～10-12, in addition to HFO-1123 and CF ₃ I, and HFC-125, HFC-134a, and HFC-32 to prepare a working medium in a mixing ratio shown in Table 21. Table 21 shows the results of measuring and calculating the temperature gradient, the discharge temperature difference, and the refrigerating cycle performance (relative refrigerating capacity and relative coefficient of performance) by the above method.

[Examples 2-17, 3-21, 4-31, 5-28]
In addition to HFO-1123 and CF ₃ I, the HFC-125, HFC-134a, the following working medium of a mixture of HFC-32 or HFO-1234yf, in the proportions shown in Table 22, in the manner described above, measuring the incombustible The calculated results are also shown in Table 22.

The composition for a heat cycle system of the present invention and the heat cycle system using the composition are freezing / refrigerating equipment (built-in showcase, separate showcase, commercial freezer / refrigerator, vending machine, ice maker, etc.). , Air conditioners (room air conditioners, package air conditioners for stores, package air conditioners for buildings, package air conditioners for equipment, gas engine heat pumps, air conditioners for trains, air conditioners for automobiles, etc.), power generation systems (waste heat recovery power generation, etc.), heat transport It can be used for equipment (heat pipes, etc.).
The specification, claims, drawings and abstracts of Japanese Patent Application No. 2018-186916 filed on October 1, 2018 and Japanese Patent Application No. 2018-193586 filed on October 12, 2018. The entire contents of the above are cited here and incorporated as disclosure of the specification of the present invention.

10 ... Refrigeration cycle system, 11 ... Compressor, 12 ... Condenser, 13 ... Expansion valve, 14 ... Evaporator, 15, 16 ... Pump

Claims (12)

1,1,2-trifluoro-ethylene, CF ₃ I and hydrofluorocarbon, the 1,1,2 comprises at least one compound selected from the hydrofluoroolefin and hydro carbon other than trifluoroethylene, a temperature gradient is 7 A composition for a thermal cycle system, which comprises a working medium for a thermal cycle having a temperature of ° C. or lower. The composition for a thermodynamic cycle system according to claim 1, wherein the hydrofluorocarbon is difluoromethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane or fluoroethane. The composition for a thermodynamic cycle system according to claim 1 or 2, wherein the hydrofluorocarbon is difluoromethane. The composition for a thermodynamic cycle system according to claim 1 or 2, wherein the hydrofluorocarbon is pentafluoroethane. The composition for a thermodynamic cycle system according to claim 1 or 2, wherein the hydrofluorocarbon is 1,1,1,2-tetrafluoroethane. The composition for a thermodynamic cycle system according to claim 1 or 2, wherein the hydrofluorocarbon is fluoroethane. The hydrofluoroolefins are 2,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene, trans-1, The composition for a thermal cycle system according to any one of claims 1 to 6, which is 2-difluoroethylene or cis-1,2-difluoroethylene. The composition for a thermodynamic cycle system according to any one of claims 1 to 7, wherein the hydrocarbon is propane. The composition for a thermodynamic cycle system according to any one of claims 1 to 8, wherein the content of the hydrofluorocarbon is 10 to 30% by mass. The composition for a thermodynamic cycle system according to any one of claims 1 to 9, which is nonflammable. A thermodynamic cycle system using the composition for a thermodynamic cycle system according to any one of claims 1 to 10. The heat cycle system according to claim 11, wherein the heat cycle system is a refrigerating / refrigerating device, an air conditioning device, a power generation system, a heat transport device, or a secondary cooler.

Images